Programming Heteropolymetallic Lanthanide Helicates: Thermodynamic Recognition of Different Metal Ions Along the Strands

Abstract

Supporting information for this article is available on the WWW under http://www.chemeurj.org/ or from the author. Table S1 lists the ESI-MS peaks, and Table S2 the 1 H NMR signals observed for mixtures of the heterotrimetallic complexes [(Ln 1) x (Ln 2) 3Àx (L9) 3 ] 9 + in acetonitrile. Tables S3 and S4 list experimental and S5 calculated mole fractions for the heterotrimetallic complexes obtained under different stoichiometric conditions. Table S6 collects structural data for the triple-helical cation in the crystal structure of [La 0.96 Eu 2.04 (L9) 3 ](CF 3 SO 3) 9 (CH 3 NO 2) 9 (1). Figures S1 and S2 show ESI-MS and 1 H NMR spectra obtained for different stoichiometric ratios Ln 1 :Ln 2 :L9. La 0.96 (L9) 3 ](CF 3 SO 3) 9 (CH 3 NO 2) 9 (1, Eu 2.04 La 0.96 C 207 H 222 N 48 O 51 S 9 F 27 , monoclinic, P2 1 /c, Z = 4) in which the cation [EuLaEu(L9) 3 ] 9 + is the major component in the crystal. The scope and limitation of this approach is discussed together with the conditions for explicitly considering intermetallic interaction parameters u Ln1Ln2 in more sophisticated chemical models.

A Simple Thermodynamic Model for Quantitatively Addressing Cooperativity in Multicomponent Self‐Assembly Processes—Part 2: Extension to Multimetallic Helicates Possessing Different Binding Sites

“…[6,7] Each ligand Lk possesses three adjacent binding segments (p = 3), which are bidentate for L4 and L5 (denticity: dent = 2), and tridentate for L6 (denticity: dent = 3). Consequently, the maximum valency v = CN/dent amounts to 4/2 = 2 for …”

“…[1] In the second section, Equation (1) is used for unravelling the assembly process of the more complicated trimetallic triple-stranded helicate [Eu 3 (L6) 3 ] 9 + , in which the central N 3 binding site is now significantly different from the terminal N 2 O sites. [6][7][8] According to the considerable amount of parameters required for assigning a specific affinity to each binding site, the simultaneous fit of bimetallic [Eu 2 (Lk) 3 ] 6 + (k = 1, 2) [9,10] and trimetallic [Eu 3 (L6) 3 ] 9 + complexes, containing common binding sites, is an attractive solution for reaching enough experimental data.…”

Linear Polynuclear Helicates as a Link between Discrete Supramolecular Complexes and Programmed Infinite Polymetallic Chains

“…We thus calculate l = 16·27·4 = 1728 microspecies characterizing the complex [Eu 4 (L4) 3 ] 12 + , while there is only r = 1 way for dissociating the final helicate to give the separated reactants. The partial statistical factor is thus simply obtained w 3m + (k = 1, 2), [8,9] and the trinuclear [Eu m (L3) n ] 3m + helicates" [10,21] with now adequate statistical factors, provides a novel set of five microscopic parameters (Table 1, Table 3, columns 4 and 5).…”

The effects of counter anions on the dynamic mechanical response in polymer networks crosslinked by metal–ligand coordination

“…34 We chose lanthanide ions because we expect the effects of counter anions would be prominent in systems with lanthanide ions-bipyridine interactions, owing to that the trivalent lanthanide ions-ligand coordination are predominately ionic in nature, with a strong preference for negatively charged ligands, rather than neutral ligand bipyridine. 35 The Eu 31 , Tb 31 lanthanide ions are chosen because of their similar ionic radii and comparable interaction strength with bipyridine ligand.…”